Nu-(decachloro-3-hydroxypentacy-clo(5.3.0.02, 6.04, 10.05, 9) decyl-3) amides



r 3,391,172 July 2, 1968 N (DECACHLORO 3 HYDROXYPENTACY- CL(5.3.0.0 .0 .0 )DECYL-3)AMlDES Edward D. Weil, Lewiston, and Keith J. Smith, Lockport, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Continuation-impart of application Ser. No. 97,771, Mar. 23, 1961. This application Nov. 30, 1965, Ser. No. 510,704

7 Claims. (Cl. 260-404) where R is a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, R is a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, amino, substituted amino, alkoxy, and aryloxy with at least one of R and R being selected from the group consisting of higher alkyl for R, or from the group consisting of higher alkyl, and higher alkylene for R; X is an element selected from the group consisting of sulfur and oxygen, oxygen being preferred for reasons of cost and, generally, stability.

The group R or R may be of high molecular weight and either or both may in fact represent macromolecular chains; and the compositions of the invention may, therefore, be macromolecular (polymeric) substances as well as lower molecular weight substances.

For the sake of simplicity the below portion of the generic formula given previously will be referred to as 10 10( c r/ r cl c c (3 equals c ocl owli) 0H C G G 1 I Cl C]. 01. C W C Among the many compounds intended to be included within the scope of this invention are the following compounds. Because of the unsettled and difiicult nomencla- KR 3.39.1..t't2 MW 6" o A 5) 3)"?? ture, the compounds are represented structurally rather than by names.

CCl1o(OH)-N CHrN CHr X and related structures.

In the latter five structures x represents the degree of polymerization, greater than one and with no upper limit. These macromolecular products of the invention may be made by the same general process as the lower molecular weight products, and are characterized by the same type of antifouling activity, while at the same time retaining certain of the desirable physical properties of the parent macromolecular compound, such as the ability to form films. Being resins, these products may serve not only as antifouling components of marine paints but also as filmforming or film-reinforcing ingredients.

The foregoing list of compounds is merely intended to be illustrative of the scope of this invention and is not in any sense intended to limit or define the invention.

While the causes of marine fouling are presently obscure, its effect on economic and military affairs is readily apparent. It is estimated that the cost of preventing, slowing down and treating marine fouling runs into millions of dollars annually, and no satisfactory solution is in sight. For example, the efficiency and the period of use of a pier, ship, boat, buoy or marine structure is greated reduced unless some prophylactic treatment is followed. Ships which have become encrusted with marine organisms lose a substantial part of their normal speed and mechanical efficiency. Furthermore, many ships and marine structures such as bulkheads, buoys, off-shore radar towers and oil drilling rigs and platforms once fouled are much more prone to become corroded or rotted. For this reason, an extensive and costly program of propylaxis and maintenance is followed in an effort to cut down the even more extensive and costly program of prophylaxis and main- The most common method of reducing the amount of the shell-like encrustation built up by the lower forms of marine life such as barnacles or other lower marine creatures is to paint the material to be protected with a special copper oxide based paint. However, the amount of copper oxide required adversely effects the physical characteristics of the paint and its normal life is reduced. In addition, the presence of a large quantity of copper oxide on a metal boat or ship will eventually create an electrolytic cell which greatly accelerates the tendency toward corrosion. To prevent this electrolytic corrosion the surface must first be covered by an additional and expensive coat of paint to insulate the copper oxide from the hull. But even when so protected, the hull of any ship or boat must be routinely scraped to remove the fouled surface which forms though albeit more slowly. Obviously too, this is expensive, since in addition to requiring costly and time-consuming dry-docking, scraping and repainting, the ship is removed from profitable use. For the above reasons, it can readily be seen that the discovery of compounds possessing antimarine fouling properties at low concentrations is of extreme commercial and naval importance. While the mechanism by which the compounds of this invention retard marine fouling is not understood, it has been found that these compounds function well at economically feasible concentrations, are noncorrosive in themselves and being readily compatible with the oils, bases and adjuvants commonly used in paints can readily be formulated in marine paints and coatings in general.

While the compounds of this invention are advantageous as antimarine fouling agents, they possess in addition other important advantages. For example, the novel compositions of this invention are useful asfige retardants i and mil d ew retardants whenformulated in orgauigfiqat- Menu...

ings.

In addition, these compositions may be used as intermediates in the preparation of other antifouling compositions. Thus, when is heated with an excess of phthalimide, the product,

is produced. This compound also has activity as a marine antifouling substance.

A related but ancillary advantage that the compounds of this invention possess generally is that they are valuable intermediates for organic synthesis, in that the reactive and free OH group may be further replaced by NRC(=X)R' where R, R and X have the same meaning as previously defined.

A further attribute that these compounds possess as synthetic intermediates is that in many instances they form complex addition compounds with water, amines, and even with additional moles of amide beyond the stoichiometrically combined amount. This characteristic is believed to be due to the ability of the -OH group to form a hydrogen bond with an electron-rich atom, particularly with a divalent oxygen atom or a trivalent nitrogen atom. For example, the product C Cl (OH NHCHO when dissolved in an excess of formamide, and the solution then poured into water, forms a more or less hydrated solid complex approximating to C Cl (OH)NHCHO NH CHO -H O A further characteristic of the new compounds of the invention is that they have weak acidic properties, perhaps due to the OH group but also in some cases perhaps due to the NH CO group. Regardless of the theoretical reasons, it has empirically been found that strong bases such as sodium methoxide, hydroxide, and the like can form salts with the compounds of the invention. Since the above mentioned salts and complexes can revert to the parent compounds of the invention, they constituted usable formulations for the purposes of antifouling coatings, a fact which we have empirically confirmed.

The novel compounds of this invention may be prepared by reacting hexachlorocyclopentadiene with chlorosulfonic acid, then heating the intermediate that forms in an appropriate solvent with at least one molar equivalent of an amide or thioamide of the structure NHRC(=X)R' The amide NHR(C=X)R may be added at the beginning of the heating, gradually during the heating, or after the heating has commenced for several hours. The rate and order of addition has not been found to be a critical feature of our process. It has also been found possible to employ polymeric compounds having a free end reactive structure NHRC(=X)R as reactants, for example, proteins, nylon, partially or fully hydrolyzed acrylonitrile polymers or copolymers and the polyurethanes. Starting with macromolecular amides, macromolecular products are obtained. It is not necessary to use a solvent for the reaction when the amide NHRC(=X)R' is a liquid or low melting solid, but where the amide is not easily fused, a solvent is convenient. Appropriate solvents include but are not limited to chlorinated hydrocarbons, such as chlorobenzene or acetylene tetrachloride, aliphatic and aromatic compounds such as cyclohexane, xylene or toluene; ketones such as methyl ethyl and methyl propyl ketone, ethers such as diethyl, dipropyl, isobutyl, nitrohydrocarbons such as the nitrobenzenes, esters such as the lower alkyl acetates, N,N-dialkylamides such as dimethyl formamide and acids such as formic acid. Where the NHRC(=X)R is a liquid the solvent may be dispensed with using an excess of the amide or thioamide instead. The temperatures needed to initiate and continue this reaction are not critical and vary considerably according to the reactants used. However, the extremes have been found to be from about zero degrees centigrade to two hundred degrees centigrade with a satisfactory range generally being between twenty degrees and one hundred and seventy-five degrees centigrade. Similarly, the time for the reaction to become complete, as measured by infra-red analysis, varies according to several factors such as temperature and reactants. Many reactions are completed in less than an hour, but others occasionally take as long as a day. The reaction may also be followed by checking the rate of S which is evolved, the reaction being halted when the flow of S0 has substantially ceased. A variation of the above process is to use a nitrile or imide capable of being hydrolyzed to the desired amide NHR(C--X)R' plus at least the stoichiometric quantity of water required for said hydrolysis, the hydrolysis being run concurrently with the reaction of the invention. The structures of the products are proved by elemental analysis by infra-red spectra which shows the OH group absorption and the characteristic amide C"O or thioamide C=S bands. The presence of the pentacyclo(5.30.0 .0 .0 )decane skeleton is proved by fusion with several parts by weight of PO1 in a sealed tube at elevated temperatures, which yields the known dodecachloropentacyclo(5:3.0.0 .0 .0 )decane melting point four hundred and eighty-five degrees. A more detailed discussion of the process and compositions produced is presented in the examples which follow.

Example 1.Preparation of C Cl (OH)(NHCOCI-I Hexachlorocyclopentadiene is reacted with chlorosulfonic acid as disclosed in US. Patent 2,516,404, an intermediate (described in said patent as C H O SCl is formed which has a melting point of one hundred and forty-six to one hundred and forty-eight degrees centigrade. This intermediate is a definite chemical entity of melting point one hundred and forty-six to one hundred and forty-seven degrees and having a chlorine content of 67.8 percent and sulfur content of 5.09 percent. Because of its high molecular weight (six hundred and eleven to six hundred and thirty-nine) 'and difficult combustibility, the number of hydrogen atoms in the molecule is in doubt, and consequently its exact structure i uncertain. A solu' tion of 62.8 parts by weight of this compound and 5.9 parts by weight of acetamide in one hundred and seventysix parts by weight of xylene is refluxed for six hours until evolution of S0 had substantially dwindled. The solution is concentrated and the'resultant crystalline product removed by filtration and dried in air. An infrared spectrum showed the compound to have an OH group, an NH group, an amide C=O group, and a methyl group.

Analysis.-Calcd. for C CI (OH)(NHCOCH Cl, 64.5; N, 2,5. Found: Cl, 63.5; N, 2.5.

Upon heating the product for twenty-four hours at three hundred degrees centigrade'with an excess of phosphorus penatchloride in a sealed tube, and evaporating the reaction mixture under vacuum at one hundred degrees centigrade, the volatile substances are removed leaving a crystalline substance which upon recrystallization, melts at four hundred and eighty-five degrees centigrade, which is the melting point of the expected and known derivative dodecachloropentacyclo(5.3.0.0 0" .0 )decane, and has the correct percentage of chlorine for 0 C1 Example 2.Preparation of C Cl (OH) (NHCHO) -NH CHO hydrate C Cl (OH) (NHCHO) -NHCHO-H O CI, 59.7; N, 4.7. Found: Cl, 60.7; N, 4.5.

Example 3.Preparation of mC ro( ig zoHzggg fig fi) 62.8 parts by weight of the product of hexachlorocyclopentadiene and ClSO H, melting at one hundred and forty-six to one hundred and forty-eight degrees centigrade, of Example 1, is refluxed one day with 11.3 parts by Weight of 2-oxahexamethyleneimine(caprolactam) in one hundred and seventy-six parts of xylene. On cooling to room temperature, there precipitates a colorless crystalline material, the infrared spectrum of which shows OH, lactam (:0, but no NH, which is the spectrum one would expect for the desired product.

Analysis.Calcd. for

C nO1 0(0H)(NCOOH CHZCHZCHQCH CHzZ N, 4.0; 01, 50.7.

Found: N, 3.6; Cl, 48.6.

Example 4.Preparation of C Cl (OH) (NHCOC H In two hundred and sixty-four parts of xylene, 12.1 parts by weight of benzamide is reacted with 62.8 parts by weight of the crystalline C Cl /ClSO H product, melting at one hundred and forty-six to one hundred and forty-eight degrees. After four hours, the S0 evolution dwindles. On partial evaporation of the xylene and cooling, a colorless crystalline product is obtained whose infra-red spectrum showed OH, NH and amide C=O groups as well as C=C double bond vibrations characteristic of an aromatic ring.

Analysis.Calcd. for C Cl (OI-I)(NHCOC H C], 58.0; N, 2.3. Found: Cl, 57.9; N, 2.3.

It is found possible to titrate the product in acetone solution using tetrabutylammonium hydroxide (OJ-N) as the base. The end point occurs at the point where one molar equivalent of the base is added, showing that the Example 5.--Preparation of C Cl (OH)NHCOC H As above, using 61.8 parts of oleamide (ten percent molar excess). The residue on evaporation of the xylene is a liquid and cannot be induced to crystallize.

The infra-red spectrum confirmed that the product has the C Cl (OH)NHCO(CI-I CH=CH(CH CH structure.

Example 7.--Preparation of C Cl (OH)N(COCH )C H A mixture of 62.8 parts of the crystalline reaction product of C 01 and C1SO H is heated with 13.5 parts of acetanilide in one hundred and eighty parts of xylene at reflux for six hours, until S evolution dwindles. Cooling to room temperature gives a crystalline precipitate, 30.5 parts by weight. Its infra-red spectrum shows the characteristic amide carbonyl band at six microns.

Analysis.Calcd. for C Cl (OH)N(COCH )C H CI, 56.7. Found: Cl, 57.9.

Example 8.Preparation of C Cl (OH)NHCI-IO A mixture of 31.3 parts of the crystalline reaction product of C Cl and CISO H in one hundred and seventysix parts of xylene, mother liquor from a previous preparation of C Cl (OI- )NHCHO, is refluxed for several hours, then while maintaining reflux, 9.0 parts of formamide is added and reflux continued for thirty hours. The mixture is then cooled to twenty to thirty degrees, and the resulting crystalline precipitate filtered off. The mother liquor is employed for a repeat run. The crystalline precipitate melts at three hundred and thirty-six degrees.

Analysis.Calcd. for C Cl (OH)NI-ICHO: N, 2.6. Found: N, 2.6.

Example 9.Preparation of A mixture of 62.8 parts of the crystalline product of C Cl and ClSO I-I and 26.8 parts of furfuramide in one hundred and seventy-six parts of xylene are refluxed for one day at the end of which time S0 evolution is negligible. On cooling, dark amorphous precipitate is formed which is filtered and dried. The infra-red spectrum supports the structure, although some complex or entrained furfuramide appeared to be present. The product is used in the crude form.

8 Analysis.-Calcd. for

Found: N, 4.2.

Example 10.Preparation of C Cl (OI-I)NHCOCH C H A mixture of 62.8 parts of the crystalline product of C Cl and CISO H in one hundred and seventy-six parts of xylene is refluxed for one day with 13.5 parts of uphenylacetamide. On cooling, a precipitate is obtained which, by infra-red, is established to have the desired C Cl (OI-I)NHCOCH C H structure.

Analysis.Calcd. for C Cl (OH) NHCOCH C H N, 2.2. Found: N, 2.5.

Example 11.--Preparation of C Cl (OH)- substituted polyamide Thirty-one parts of the crystalline product of C Cl and chlorosulfonic acid is pulverized with thirty parts of a commercial polyamide derived from ethylenediamine and a fatty dibasic acid C H (COOH) and the mixture is heated at one hundred and forty to one hundred and fifty degrees for eighteen hours, at which time no further S0 was evolved. The product is cooled and the resulting resin is pulverized. The infra-red spectrum establishes the presence of the C Cl (OH)NRCOR' structure.

Example 12.-Preparation of other representative compounds of this invention The chlorosulfonic acid intermediate of hexachlorocyclopentadiene melting at one hundred and forty-six to one hundred and forty-eight degrees centigrade is reacted with the appropriate amide as disclosed in the preceding examples. The following compounds are prepared (left hand column), in crude form. The right hand column gives the amides used.

Compound Derived From- C CIm(OH)NH-COCH=CHZ Aerylamide. CmCl10(OH)-NHC0CHzCl Chloroacetarnide. CIOOIIQ(OH) NHCOOHOHCH3 Laetamide. C CIw(OH)NH-COCCI Trichloroaeetamide. C10Cl|n(0H)NHCOCHZCHzCHzCHg Adiparnide.

CONH(CmClio(OH)) CIUCIID(OH)NHCO Salieylamide.

| HO (C,Cho(OH)-NHCO)2- Phthalamides.

CrnClro(OH)NHCONI-Iz Carbamide.

CioC1ro(OH)NHCO-O CzH5 CMChowm-NHGOo-Q Ethyl urethane.

Phenyl urethane.

CH; O oCl1o(0 H) N\ N-methyliormamido.

O HO

0 H 0 "101M 0 H) N N-mcthylstearamide.

CO (CH2)1BCH3 CzHs N ethylbenzamide.

Maleimide.

Compound Derived From- C OC H2 CmC11o(0 H) N Suecinimide.

O O C Hi CwCl1o(0H)N /OO Dimethylhydantoin.

C O-NH CmClm(OH) -N Phthalimide.

CCl1o(OH)-N\ Nylon 6". C x

C1oCl10(O H) N\ 2)4 Nylon 66". /C 0 010 110 L x /C ONH ioCl1o( H) Urea formaldehyde resins.

C Ha-N CH9- X and related structures.

Example 13.Formulati0n of marine aint having antifouling properties The following ingredients are blended and ground together in a ball mill.

Ingredient: Pounds per 100 gallons Gum rosin, grade WW 277 Blown fish oil 118 Zinc stearate 18 Versamide polyamide adduct of Example 11 197 w Zinc oxide 161 Magnesium silicate 56 Solvent naphtha, approx. 241 Lampblack 1 1 Volume adjusted to 100 gal. by addition of naphtha.

Example l4.Formulation of marine paint having antifouling properties The following ingredients are blended and ground together in a ball mill.

1 Volume adjusted to 100 gal. by addition of naphtha.

Example 15 .Formulation of marine paint having antifouling properties As above, using in place of C Cl (OH)NHCOC H the product C Cl (OH)NI-ICHO-NH CHO hydrate of Example 2.

Example 16.Formulation of a marine paint having antifouling properties The following ingredients are blended together in the indicated proportions, in a ball mill.

Pounds per gallons Ingredient:

Rosin 265 Coal tar 80 Talc Q 80 Pine oil 42 C Cl (OH) (NHCOCH from Example 1 200 High flash naphtha Mineral spirits, make up to volume.

Example 17.Another formulation of marine paint having antifouling properties Xylene, remainder.

Example 18.--Testing of paint formulations of the preceding examples for antifouling properties The formulations disclosed in the preceding examples are painted on steel test panels, allowed to dry and immersed in sea water at a subtropical location. At the same time other identical panels are painted with control test formulations identical with these paint preparations except that the N-decachlorohydroxypentacyclodecylamide derivatives are omitted from the formulation. These test panels are immersed in the same subtropical sea water. After one month both the control test panels and the panels containing the active component are examined and compared. It is found that the control panels are heavily crusted with a mixed population of barnacles and other marine organisms, while the panels containing the active antimarine fouling component were not adversely affected.

Example 19.Testing of antimarine fouling properties of different products of this invention To eliminate variables due to the other ingredients in the paint formulations a simplified comparison test is carried out by treating porous test panels with a number of the products of this invention applied as a three percent solution of methyl isobutyl ketone. The panels are allowed to dry and are then immersed in sea water at a subtropical location where untreated test panels became heavily fouled during the test interval. After a one month period the degree of fouling control was observed according to the amounts of fouling organisms found on the treated panel surface compared to identical untreated panels. The results are recorded on Table I below.

Compound Algae Amphi- Annelida Barnacles B ryozoa I-Iydroids Mollusks Tunicates Micro pods 1 ulmg C|nCl1o(OH) (NHCHO) 100 100 100 100 100 100 100 100 100 K C|uCl1o(OH) (NHCOCH 100 100 100 95 100 100 100 100 100 CwCl|o(O H) (NHCO CeHs) 100 100 100 100 100 100 100 100 100 CwCl1u(OH) (NHCOCHZC H 50 100 100 100 100 100 100 100 90 C|oC11u(OH)(NHCONH2) 0 20 0 0 50 100 50 0 C O 100 100 100 100 95 100 100 100 100 C nCl(OH) NH I C 0 What is claimed is:

Cl Cl )b wherein M is selected from the group consisting of CH and O, and a and b are from zero to one; alkylene of from 1 to 22 carbon atoms; ami'o; and lower alkoxy; wherein Qiis selected from the group consisting of oxygen and sulffi provided that when R is not highly alkyl, of 12 to 22 c rbon atoms, R is selected from the group consisting of higher such alkyl and higher alkylene, of 12 to 22 carbon atoms.

2. A compound according to claim 1 wherein oxygen.

3. A compound according to claim 2 in which only R is higher alkyl of 12 to 22 carbon atoms.

4. A compound according to claim 2 in which both R and R are higher alkyl of 12 to 22 carbon atoms.

5. A compound according to claim 1 wherein R is hydrogen, and R is C H 6. A compound according to claim 2, wherein R is hydrogen, and R is (CH2)7CH=CH(CH2)7CH3.

7. A compound according to claim 3, wherein R is CH and R is (CH CH Xis No references cited.

NICHOLAS S. RIZZO, Primary Examiner.

CHARLES B. PARKER, Examiner.

A. SUTTO, F. MIKA, Assistant Examiners. 

